High performance silicon-based coating compositions

ABSTRACT

A silicon-based coating composition for a wide range of mold surfaces, which composition is formed from a mixture of constituents comprising appropriate portions of silazane, siloxane, and silane, and optionally organic solvent. The composition, after curing, results in an extreme release product that is non-transferable to the finished part, allowing for proper adhesion of coatings or adhesives to the finished surface without additional surface preparation. The cured coatings are ultrathin, having a thickness between 0.1 μm and 3 μm, and having a hardness between about 4H and about 9H.

CROSS REFERENCE

This application claims the benefit of the filing date as a divisionalof the U.S. patent application Ser. No. 15/395,642, filed on Dec. 30,2016, now allowed, which is a continuation of the U.S. patentapplication Ser. No. 13/935,443 filed on Jul. 3, 2013, now U.S. Pat. No.9,567,488, which claims the benefit of priority of U.S. ProvisionalPatent Application Ser. No. 61/667,559 filed Jul. 3, 2012, thedisclosures of which are each incorporated by reference in theirentireties for all purposes.

FIELD OF THE INVENTION

The present invention relates to silicon-based coating compositionsformed from silicon monomers and macromers, such as silazanes,siloxanes, silanes, and optionally, organic and inorganic substituents,solvents and additives. The resultant composition can be used forcoating a surface to form coatings having desired features includingvariable coefficient of friction characteristics, excellent moldrelease, high temperature and high heat resistance, and good hardness.Such coatings are useful in a wide range of applications.

BACKGROUND OF THE INVENTION

Chemical structure and conformation of a polymer are among the manyfactors that influence the type of coating required for a particularapplication. However, the commercial availability of many usefulpolymers often limits the applications. For example, for a long timepolysilazanes have been synthesized and characterized, whichacknowledges that such a polymer could be useful in a variety ofapplications. Currently, however, few products have been developed intoa marketable commodity due to the extensive and costly synthesis neededto form the base resin products. In addition, the previous process hadtoxicity issues, for example, the formation of toxic ammonium salts andhydrochloric acid, which limits the availability of finished,user-friendly products.

An improved silicon-based coating is needed for use in a wide range ofapplications. Such coatings would be moisture and air curable at ambienttemperature conditions without requiring an added catalyst or activatorfor rapid curing, or can be cured at elevated temperatures to increasethe glass transition (Tg) properties of the finished product byenhancing the degree of crosslinking. Other advantageous characteristicsof an improved silicon-based coating include being thin but durable,protective and heat-stable, displaying excellent hardness (for example,having a hardness of 5H or above), remaining intact even when thesubstrate is deformed. In addition, coatings that are customizable interms of coating color, appearance, transparency, feel, and glossinessare desirable. Further, coatings being UV resistant, microbialreleasable, easy to clean and maintain, and corrosion resistant are alsoin great need for their wide range of uses.

Another common problem in applying silicon-based coating relates to moldrelease coatings. Currently, many mold release problems are associatedwith a mold or surfaces of a molded part. For example, when the molddoes not allow for a complete release, the removal of the molded part ismuch more difficult, such that mold or part surface will likely bedamaged. Although one can use a release agent to facilitate the moldrelease, the release agent can result in resin build-up which causesphysical tolerance alteration to the fabricated parts, and/or poorcosmetic appearance of the parts. Release agent build-up also creates aninterrelated physical roughness and chemical reactivity of mold cavitysurfaces. The friction of the rough surface then causes resin tocontinue to attach and stick to the cavities, crevices, pits or pores ofthe surfaces of the mold and the molded part. As a result, scrappingand/or sanding are subsequently required which lead to more and largerscratches, cavities or pitting on the mold surface that increasecoefficient of friction. The increased coefficient of frictionnegatively affects the release of the molded part from the mold, thephysical tolerance and appearance of the finished part, and thetransferring of the release agent to the finished part. Additionally,the transfer of substances in the mold release coating to the surfacesof molded part is also a profound problem, which surface contaminationcreates problems of adhesion for applying primers and finish coats tothe molded part.

Therefore, given the limitations of the prior art, it is desirable tohave a coating composition that has superior release properties, suchthat the resultant coating has improved physical and chemical resistantproperties and results in an easy- and simple-to-apply coating productpossessing a number of desirable properties, including, but not limitedto, 100% non-transferable, extended coverage, ultrathin, low odor,recoat-able, high heat and temperature resistant, applicable to highertemperature cures, for example, 1400° F. or higher, which constitutesuperior mold release characteristics than the current release products.Such coating provides an ultrathin barrier that prevents release agents,resins, substances, or other coatings from securing themselves to themolded part surface, crevices, indentations and/or micro-pores, andprevents surface contamination that may interfere with bonding betweencoatings, adhesives or the like and the surface of a finished part.

SUMMARY OF THE INVENTION

The present invention relates to silicon-based coating compositions,methods for applying the coating compositions, and coatings, typicallycured coatings, formed from those compositions. These coatings areapplicable to a wide range of surfaces, especially to molds, where easyrelease of the molded article is desired without also transferring ordestroying the coating on the mold. The coating compositions of thisinvention, however, are not limited to molds, and may be applied to anysurface where the properties of the cured coating are desired. The curedcoating has a thickness between about 0.1 μm and about 40 μm and extremerelease properties, is non-transferable, long-lasting, and can withstandhigh pressure, high temperature and/or extended temperatures withoutsacrificing the extreme release properties. As such, the cured coatingallows for extended usable coverage, lower material usage, lessre-coating application effort and time, reduced de-mold labor, time andeffort, and thus much lower associated costs.

The coating composition is a mixture of constituents comprisingappropriate portions of silazane, siloxane, silane, and optionally,organic solvents and other additives. The constituents may be monomers,macromers, oligomers, or polymers. This mixture is advantageouslycapable of curing under ambient conditions at room temperature withoutadded heat, catalysts, or other additives, thereby forming a coatingthat is substantially free of unreacted Si—H bonds, and which contains acrosslinked polymer network comprising Si—O, Si—C, and Si—N bonds.Durability in particular is due to the prevalence of Si—C bonds in thecrosslinked network structure of the coating. These coating compositionsallow for a lower concentration of silazane resins in the formulation,increased penetration to the substrate, thereby reducing the cost,simplifying the steps of mixture preparation and processing, decreasingodor of the finished coating products, and greatly improving thedurability of the cured coating.

In particular, the current invention relates to silicon-based coatingcompositions, which after curing, provide a mold release coating withsuperior release properties. The cured mold release coating may be 100%non-transferable to a finished composite part, can withstand hightemperatures and high pressures, may have a thickness ranging betweenabout 0.1 μm and about 40 μm, have a coefficient of friction betweenabout 0.03 and about 0.04, and have a hardness ranging between about 4Hand about 9H. The composition may be formed from a mixture ofconstituents comprising between about 0% (w/w) and about 76% (w/w)silazane, between about 0.2% (w/w) and about 4% (w/w) siloxane, andbetween about 1% (w/w) and about 9% (w/w) silane. These coatingcompositions may be applied to a substrate by any known method, inparticular by transferring the coating composition to a substrate bywiping. The coating composition then cures to form a cured coating,preferably under ambient atmospheric conditions without added heat orcatalyst.

Several embodiments capture particular ratios of constituents in thecoating composition. In one embodiment, the silicon-based coatingcomposition comprises between about 4% and about 12% (w/w) silazane,between about 0.2% and about 0.6% (w/w) siloxane; between about 4% andabout 7% (w/w) silane, and between about 80% and about 92% (w/w) organicsolvent prior to curing. In another embodiment, the silicon-basedcoating composition comprises between about 1% and about 4% (w/w)siloxane, between about 1% and about 4% (w/w) silane, and between about92% and about 98% (w/w) organic solvent. In yet another embodiment, thesilicon-based coating composition comprises between about 45% and about55% (w/w) silazane, between about 1% and about 3% (w/w) silane, andbetween about 42% and about 54% (w/w) organic solvent. In otherembodiments, the silicon-based coating composition comprises betweenabout 56% and about 76% (w/w) silazane, between about 0.7% and about 1%(w/w) siloxane, between about 1% and about 2% (w/w) silane; and betweenabout 21% and about 43% (w/w) organic solvent. In still anotherembodiment, the silicon-based coating composition comprising betweenabout 7% and about 11% (w/w) silazane, between about 0.2% and about 0.6%(w/w) siloxane, between about 5% and about 9% (w/w) silane, and betweenabout 79% and about 89% (w/w) organic solvent.

In addition, the present invention further provides a method of coatinga surface. The method comprises mixing a mixture of constituents to forma silicon-based coating composition comprising, for example, from about0% (w/w) to about 76% (w/w) silazane, from about 0.2% (w/w) to about 4%(w/w) siloxane, and from about 1% (w/w) to about 9% (w/w) silane. Next,the mixture is coated onto a surface and curing the coating ambientlywith or without additional heat. This method may be applied to mixingany silicon-based coating composition described herein, and may beapplied to any surface.

The present invention also provides a cured silicon-based coating. Thecoating is formed from a mixture of constituents comprising from about0% (w/w) to about 76% (w/w) silazane, from about 0.2% (w/w) to about 4%(w/w) siloxane, and from about 1% (w/w) to about 9% (w/w) silane. Thecoating is substantially free of Si—H bonds. The coating also comprisesa polymer network comprising Si—O bonds and Si—C bonds. In furtherembodiments, the coating may be non-transferable, has a thicknessranging between about 0.1 μm and about 3 μm, have coefficient offriction between from about 0.03 to about 0.04, and have a hardnessranging between about 4H and about 9H.

BRIEF DESCRIPTION OF THE FIGS

FIG. 1 depicts the result of differential thermal analysis (DTA) ofDT-6060 and DT-420 coatings tested from 25° C. to 650° C. The plot forDT-420 is shown in dark gray and the plot for DT-6060 is shown in lightgray.

FIG. 2 depicts the Fourier transform infrared (FTIR) spectrum of aG-Shield™ (also known as “Clariant TutoProm”) coating sample.

FIG. 3 depicts the FTIR spectrum of a DT-6060 coating sample.

FIG. 4 depicts the FTIR spectrum of a DT-420 coating sample.

FIG. 5 depicts the FTIR spectrum of a DT-405 coating sample.

FIG. 6 depicts the FTIR spectrum of a DT-201 coating sample.

FIG. 7 depicts the FTIR spectrum of a HTA® 1500 coating sample.

FIG. 8 shows the dynamic light scattering (DLS) histogram for the Si—Nstarting material.

FIG. 9 shows the DLS correlogram for the Si—N starting material.

FIG. 10 shows the DLS histogram for Si—N—IS-300.

FIG. 11 shows the DLS correlogram for Si—N—IS-300.

FIG. 12 shows the DLS histogram for Si—N—MC.

FIG. 13 shows the DLS correlogram for Si—N—MC

FIG. 14 shows the DLS histogram for Si—N-D68.

FIG. 15 shows the DLS correlogram for Si—N-D68.

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to silicon-based coating compositions,methods for applying the coating compositions, and coatings formed fromthose compositions. These coatings are applicable to a wide range ofsurfaces, especially to molds, where easy release of the molded articleis desired without also transferring or destroying the coating on themold. The cured coatings, however, may be applied to any surface forprotection, including both the molding and tooling surfaces (surfaces ofthe molded part), underlying finish and/or substrates, in a wide rangeof applications.

By way of example, composite parts are often formed using vacuumbagging, where the vacuum tightly compresses the composite part whileremoving entrapped air and/or volatiles. But the mold surfaces developleaks as a result of the cyclic stresses caused by the continuedheating, cooling, and vacuum compressing. These leaks arise fromphysical deterioration of the resin and its bonds to the fibers withinthe mold tool structure. This deterioration prevents the vacuum frompulling at an adequate pressure. As the deterioration progresses, smallmicro-pores, fractures, and even cracks form, allowing air to be drawnin and pass through the mold surface and its structural substrata, thuslessening or preventing the vacuum levels needed to create appropriateproperties within the finished composite part.

The silicon-based mold release coating compositions described hereinovercome these problems. The silicon-based coating compositions absorband penetrate deeply into the areas known to contain micro-pores,fractures and cracks on the face side of the mold tool. After thecoatings cured, the possible vacuum levels increased during subsequenttesting, indicating that openings in the mold had been filed. Repeatedapplications of the coating composition onto the mold tool restored itto levels equal to or better than when the mold tool was new. Moreover,the physical dimensions of the mold tool were not measurably changed.The mold tool could maintain its vacuum integrity during normal use withthe periodic reapplication of the silicon-based coating compositions tothe surface, as is common practice in the art.

The cured coatings formed from the coating compositions are clear, thin,hard, slick, having a shortened curing process, and with resistance orhigh endurance to adverse conditions including, but not limited to,drag, pull, scrub, friction, heat, moisture, high temperature, lowtemperature, microbial growth, corrosion, and the like. These curedcoatings have superior properties to coatings formed from any of theindividual ingredients by themselves, as a result of chemical reactionsbetween the individual ingredients during curing. The cured coating hasa thickness between about 0.1 μm and about 40 μm and extreme releaseproperties, is non-transferable, long-lasting, and can withstand highpressure, high temperature and/or extended temperatures withoutsacrificing the extreme release properties. As such, the cured coatingallows for extended usable coverage, lower material usage, lessre-coating application effort and time, reduced de-mold labor, time andeffort, and thus much lower associated costs.

The compositions comprise silane and either or both of silazane andsiloxane, and may further comprise one or more organic or inorganicsubstituents, non-reactive solvents, and/or one or more additives forcuring or for finishing, each of which in a proportion as designedherein to achieve certain properties.

The silicon-based coating compositions of the present invention, priorto curing, include a silazane constituent. “Silazane” and“polysilazane,” as appearing in the specification and claims are genericterms intended to include compounds which contain one or moresilicon-nitrogen bonds in which the nitrogen atom is bonded to at leasttwo silicon atoms, and may or may not contain cyclic units. Therefore,the terms “polysilazane” and “silazane polymer” include monomers,oligomers, cyclic, polycyclic, linear polymers or resinous polymershaving at least one Si—N group in the compound, or having repeatingunits of H₂Si—NH, that is, [H₂Si—NH]n, with “n” greater than 1. Thechemical structure for polysilazane is shown below.

By “oligomer” is meant any molecule or chemical compound which comprisesseveral repeat units, generally from about 2 to 10 repeat units. Asimple example of silazane oligomer is disilazane H₃Si—NH—SiH₃.“Polymer” or “copolymer”, as used herein, means a molecule or compoundwhich comprises a large number of repeat units, generally greater thanabout 10 repeat units. The oligomeric or polymeric silazanes may beamorphous or crystalline in nature. Silazane polymer chains having bothlarge chains and small rings with a wide range of molecular mass arecalled polysilazanes. Polysilazane or a mixture of polysilazanes knownin the art or commercially available include such products generallyknown among persons skilled in the art as silazanes, disilazanes,polysilazanes, ureasilazanes, polyureasilazanes, aminosilanes,organosilazanes, organopolysilazanes, inorganic polysilazanes, andothers employing liquid anhydrous ammonia in their production. Apolysilazane with the general formula(CH₃)₃Si—NH—[(CH₃)₂Si—NH]_(n)—Si(CH₃)₃ is designated aspolydimethylsilazane. One group of polysilazane, [R₁R₂Si—NH]_(n), isisoelectronic with and close relatives to polysiloxane [R₁R₂Si—O]₁.Additionally, Si—N bond can be found in triethylsilylamine((H₅C₂)₃Si—NH₂), which is a typical aminosilane. Further, smallring-shaped molecules with a basic group of Si—N are called“cyclosilazanes.” For example, triazatrisilane (H₉N₃Si₃) is a typicalcyclotrisilazane.

A silazane constituent is commonly produced by ammonolysis of ahalosilane, such as a chlorosilane or and organochlorosilane. In thisprocess, the nitrogen nucleophilically attacks the carbon alpha to thechlorine, forming a new Si—N bond and releasing hydrochloric acid (HCl)as a byproduct. The HCl then reacts with excess ammonia in the reactionmixture, producing ammonium chloride. Because of the ammonolysisprocess, the silicon and nitrogen atoms have a preferable distributionwithin the cured coating composition.

If the silazane is not properly isolated after synthesis, the silazaneconstituent will contain residual ammonia reactant, free amine from sidereactions, and ammonium chloride byproduct. These nitrogen-containingmaterials are undesirable at least because of their environmentaltoxicity. Also, the first- and second-order elimination reaction maylead to alkyl and vinyl substituents, producing, for example,chloromethylvinylsilane, chlorodivinylsilane, dichloroethylvinylsilane,chloromethyldivinylsilane, etc., depending on the organochlorosilanestarting material. The vinyl groups are particularly an issue becausethey can react with compounds of low molecular weight that are mixedwith the constituents before curing and initiate and facilitatepolymerization reactions. These polymerization reactions increase thechain length and the degree of three-dimensional crosslinking of thepolymer networks in the cured coatings. As a result, they have muchhigher mass ranges and significantly improved material properties.

The polymerization processes include, but are not limited to,step-growth polymerization, polyaddition, and polycondensation. Morespecifically, polymerization can be initiated by mechanisms, such asacid- or base-catalysis, or free radical polymerization. It may comprisering-opening copolymerization, and the formation of inorganic and/ororganic polymer networks. The actual mechanisms of polymerization dependon the functional groups of the reacting polymeric and monomericcompounds, as well as inherent steric effects. Conceptually newmaterials can be formed by adding non-conventional starting materialsinto the polymerization process, such as ammonia.

For polymerized silicon-based materials, ammonia is used to dissolve andage the materials, which must be carefully regulated through venting tocontrol the molecular weight of the resin starting material. Thisreaction results in a R₃Si—NH₂ group to form silazane units by releasingoff the ammonia. High moisture and/or water will cause decomposition ofthe polymerized silicon-based material, due to the water moleculeattacking the silicon atoms and the Si—N bonds are then severed. Thisreaction produces a R₃Si—NH₂ and HO—SiR₃ which further react to formR₃Si—O—SiR₃ siloxane. The polymerized liquid is clear to translucent,colorless to pale yellow, and may form a solid. Exposure to highertemperature and or sunlight can also increase the mass of thepolymerized liquid by encouraging further thermal or photochemicalpolymerization. In the liquid form, trace elements, free ammonia andammonium chloride can often be detected.

“Prepolymer” refers to polymeric structures formed by the processes inthe present invention are long term-stable liquids, and possess onlymoderate odors, which mostly arise from the use of organic solvents(with acceptable toxicity, such as tert-butyl acetate). In the solidform, these polymerized materials can be handled similar tothermosetting or thermoplastic processes. Molecular weight can vary fromabout 2,000 g/mol up to as much as 100,000 g/mol, depending on process.The density of the prepolymers is normally around 1 g/cm³.

Polysilazanes usually do not vaporize due to the strong molecularinteractions. Heat promotes crosslinking of the polysilazanes to form aneven higher molecular weight structures. For example, at temperatures of100-300° C., hydrogen gas evolves and ammonia promotes furthercrosslinking. As provided in the present invention, vinyl substituentspromote continued crosslinking, increased molecular strength, andconversion of liquid resins into solids. Once temperatures reach700-1200° C., the multi-dimensional amorphous network with Si, C and Natoms is formed, resulting in SiCN ceramic. This “pyrolysis” ofpolysilazanes produces ceramic materials with low viscosity in highyield. This also makes the polysilazanes an excellent choice forprecursors for other ceramic matrices. As provided in the presentinvention, polymers combined with low molecular weight components offeradded value for the generation of resistant and fast-curing coatings,because new chains can be formed that can improve and enhance theresulting material properties.

Alternatively, polysilazane is commercially available. For example,polysilazane (<99%) in tert-butyl acetate solvent manufactured by KiONDefense Technologies, Inc. (Huntingdon Valley, PA) as KDT Ambient CureCoating Resin (KDT HTA® 1500), is supplied as a 100% solids liquid oflow viscosity. KDT HTA® 1500 may comprise more than 99% polysilazane.KDT HTA® 1500 may comprise less than 5% cyclosilazane, a cyclic form ofpolysilazane. A similar product is also available from othermanufacturers, including AZ Electric Materials (Branchburg, N.J.), theparent company to KiON.

Polysilazane as provided in the form of KDT HTA® 1500 resin may comprisebetween about 0% and about 76% (w/w) of the total formula weight ofsilicon-based coating compositions. In one embodiment, the silicon-basedcoating composition does not contain polysilazane in the form of KDTHTA® 1500 resin or the like. In some embodiments, polysilazane in theform of KDT HTA® 1500 resin or the like (A-Resin, as designated herein)comprises about 76%, 70%, 65%, 62%, 57%, 52%, 47%, 42%, 37%, 32%, 27%,22%, 12%, 10%, 8%, 5%, 4%, 3%, 2%, 1%, 0% (w/w), or any range thereof,of the silicon-based coating composition. For example, the amount ofpolysilazane, in the form of KDT HTA® 1500 resin or the like, present inthe silicon-based coating composition may range from between about 0% toabout 3%, between about 2% to about 4%, between about 4% to about 6%,between about 5% to about 8%, between about 6% to about 9%, betweenabout 7% to about 10%, between about 8% to about 11%, between about 9%to about 12%, between about 10% to about 15%, between about 12% to about22%, between about 18% to about 28%, between about 25% to about 35%,between about 32% to about 42%, between about 40% to about 50%, betweenabout 48% to about 58%, between about 55% to about 65%, between about60% to about 70%, between about 68% to about 76%, (w/w) of the totalcomposition, and preferably ranges from between about 0% to about 1%,between about 4% to about 12%, between about 6% to about 10%, betweenabout 7% to about 9%, between about 45% to about 55%, between about 56%to about 76%, between about 7% to about 11%, (w/w) of the totalcomposition. In an exemplary embodiment, the amount of polysilazane, inthe form of KDT HTA® 1500 resin or the like, present in the compositionis between about 7% to about 8%, (w/w) of the total composition. Inanother exemplary embodiment, the amount of polysilazane, in the form ofKDT HTA® 1500 resin or the like, present in the composition is 0% (w/w)of the total composition.

The silicon-based coating compositions of the present invention may alsoinclude a siloxane. A “siloxane” is a chemical compound having branchedor unbranched backbones consisting of alternating silicon and oxygenatoms —Si—O—Si—O— with side chains R attached to the silicon atoms(R₁R₂SiO), where R is a hydrogen atom or a hydrocarbon group.Polymerized siloxanes, including oligomeric and polymeric siloxaneunits, with organic side chains (R H) are commonly known aspolysiloxanes, or [SiOR₁R₂]n, wherein n is greater than 1. The chemicalstructure for a linear polysiloxane is shown below:

In addition to hydrogen, R₁ and R₂ of polysiloxane may be independentlyselected from the group consisting of alkyl, alkenyl, cycloalkyl,alkylamino, aryl, aralkyl, or alkylsilyl. Thus, R₁ and R₂ may be, forexample, methyl, ethyl, propyl, butyl, octyl, decyl, vinyl, allyl,butenyl, octenyl, decenyl, tetradecyl, hexadecyl, eicosyl, tetracosyl,cyclohexyl, methylcyclohexyl, methylamino, ethylamino, phenyl, tolyl,xylyl, naphthyl, benzyl, methylsilyl, ethylsilyl, propylsilyl,butylsilyl, octylsilyl, or decylsilyl. These alkyl, alkenyl, cycloalky,aryl, alkyl amino, aralkyl and alkylsilyl groups may each optionally besubstituted by one or more substituents which contain heteroatoms, suchas halides, like chlorine, bromine and iodine; alkoxy groups, likeethoxy, and also acyl groups, such as acetyl and propionyl. Organic sidegroups can be used to link two or more of these —Si—O— backbonestogether. By varying the —Si—O— chain lengths, side groups, andcrosslinking, polysiloxanes can vary in consistency from liquid to gelto rubber to hard plastic. Representative examples of polysiloxane are[SiO(CH₃)₂]_(n) (polydimethylsiloxane, PDMS) and [SiO(C₆H₅)₂]_(n)(polydiphenylsiloxane). In a preferred embodiment, the silicon-basedcoating composition comprises polydimethylsiloxane. The chemicalstructure for polydimethylsiloxane is shown below.

Octamethyltrisiloxane, [(CH₃)₃SiO]₂Si(CH₃)₂, is a linear siloxane in thepolydimethylsiloxane family, with the INCI name as Trisiloxane. Thechemical structure for octamethyltrisiloxane is shown below.

Other methylated siloxanes include, but are not limited to:hexamethyldisiloxane, cyclotetrasiloxane, octamethylcyclotetrasiloxane,decamethyltetrasiloxane, decamethylcyclopentasiloxane. The method ofproducing high molecular weight polysiloxane product was disclosed inUS. App. Pub. 2009/0253884. In addition, polysiloxane is alsocommercially available. As one example, polysiloxane, specifically,polydimethylsiloxane, is supplied in isopropyl acetate solvent byGenesee Polymers Corp. (Burton, MI), and it is sold as Dimethyl SiliconeFluids G-10 product. Polysiloxane as provided in the form of DimethylSilicone Fluids resin (B-Resin, as designated herein, containing up to5% polysiloxane) comprises between about 0.2% and about 4% (w/w) of thetotal formula weight of silicon-based coating compositions. In oneembodiment, the silicon-based coating composition does not containpolysiloxane in the form of Dimethyl Silicone Fluids. In someembodiments, polysiloxane, in the form of Dimethyl Silicone Fluids orthe like, comprises about 4%, 3.7%, 3.5%, 3.2%, 3.0%, 2.7%, 2.5%, 2.3%,2.1%, 2.0%, 1.9%, 1.7%, 1.5%, 1.3%, 1.1%, 1.0%, 0.7%, 0.5%, 0.4%, 0.3%,0.2% (w/w), or any range thereof, of the silicon-based coatingcomposition. For example, the amount of polysiloxane, in the form ofDimethyl Silicone Fluids or the like, present in the silicon-basedcoating composition may range from between about 0.2% to about 0.5%,between about 0.4% to about 1.5%, between about 1% to about 2%, betweenabout 1.5% to about 2.2%, between about 1.8% to about 2.5%, betweenabout 2.0% to about 2.8% (w/w), between about 2.5% to about 3.0%,between about 2.8% to about 3.5%, between about 3.0% to about 3.8%,between about 3.5% to about 4.0%, (w/w), of the total composition, andpreferably ranges from between about 0.2% to about 0.6%, between about1% to about 4%, between about 0.7% to about 1%, (w/w) of the totalcomposition. In an exemplary embodiment, the amount of polysiloxane, inthe form of Dimethyl Silicone Fluids or the like, present in thecomposition is about 0.4% (w/w) of the total composition. In anotherexemplary embodiment, the amount of polysiloxane, in the form ofDimethyl Silicone Fluids or the like, present in the composition is 2%(w/w) of the total composition. In another exemplary embodiment, theamount of polysiloxane, in the form of Dimethyl Silicone Fluids or thelike, present in the composition is 0.6% (w/w) of the total composition.In still another exemplary embodiment, the amount of polysiloxane, inthe form of Dimethyl Silicone Fluids or the like, present in thecomposition is 3% (w/w) of the total composition. In still anotherexemplary embodiment, the amount of polysiloxane, in the form ofDimethyl Silicone Fluids or the like, present in the composition is 0.8%(w/w) of the total composition. In yet another exemplary embodiment, theamount of polysiloxane, in the form of Dimethyl Silicone Fluids or thelike, present in the composition is 3.5% (w/w) of the total composition.

The silicon-based coating compositions of the present invention mayfurther include polymerized silane. Silanes are compounds which containone or more silicon-silicon bonds. Polysilanes [R₁R₂Si—R₁R₂Si]_(n) are alarge family of inorganic polymers. The number of repeating units, “n,”determines the molecular weight and viscosity of the composition. Likein polysiloxane, R₁ and R₂ are independently selected from the groupconsisting of hydrogen, alkyl, alkenyl, cycloalkyl, alkylamino, aryl,aralkyl, or alkylsilyl. Thus, R₁ and R₂ may be, for example, methyl,ethyl, propyl, butyl, octyl, decyl, vinyl, allyl, butenyl, octenyl,decenyl, tetradecyl, hexadecyl, eicosyl, tetracosyl, cyclohexyl,methylcyclohexyl, methylamino, ethylamino, phenyl, tolyl, xylyl,naphthyl, benzyl, methylsilyl, ethylsilyl, propylsilyl, butylsilyl,octylsilyl, or decylsilyl. A polymer with the general formula—[(CH₃)₂Si—(CH₃)₂Si]—_(n), is designated as polydimethylsilane. Thechemical structure of polydimethylsilane is shown below.

High molecular weight polysilane product with a narrow molecular weightdistribution may be obtained by the process of U.S. Pat. No. 5,599,892.Polysilane is also available as a resin system supplied in amyl acetateblend from Kadko, Inc. (Beech Grove, Indiana), and it is sold as aKADKLAD R2X3™ product. Polysilane as provided in the form of KADKLADR2X3 resin (C-Resin, as designated herein, containing polysilane up to8%) comprises between about 1% and about 9% (w/w) of the total formulaweight of silicon-based coating compositions. In one embodiment, thesilicon-based coating composition does not contain polysilane in theform of KADKLAD R2X3 resin. In some embodiments, polysilane, in the formof KADKLAD R2X3 resin or the like, comprises about 9%, 8.7%, 8%, 7.6%,7%, 6.7%, 6.5%, 6.0%, 5.8%, 5.5%, 5.3%, 5%, 4.7%, 4.5%, 4.3%, 4%, 3%,2%, 1% (w/w), or any range thereof, of the silicon-based coatingcomposition. For example, the amount of polysilane, in the form ofKADKLAD R2X3 resin or the like, present in the silicon-based coatingcomposition may range from between about between about 2% to about 3.2%,3% to about 4.2%, between about 4% to about 4.8%, between about 4.5% toabout 5.1%, between about 4.8% to about 5.4%, between about 4% to about4.7%, between about 4.5% to about 6.2%, between about 4.8% to about6.5%, between about 5.1% to about 6.7%, between about 5.4% to about 7%,between about 6.4% to about 7.8%, between about 7.2% to about 8.4%,between about 8.2% to about 9%, (w/w) of the total composition, andpreferably ranges from between about 1% to about 3%, between about 4% toabout 7%, between about 5% to about 9%, (w/w) of the total composition.In an exemplary embodiment, the amount of polysilane, in the form ofKADKLAD R2X3 resin or the like, present in the composition is about 5.8%(w/w) of the total composition. In another exemplary embodiment, theamount of polysilane, in the form of KADKLAD R2X3 resin or the like,present in the composition is 4% (w/w) of the total composition. Inanother exemplary embodiment, the amount of polysilane, in the form ofKADKLAD R2X3 resin or the like, present in the composition is 8% (w/w)of the total composition. In another exemplary embodiment, the amount ofpolysilane, in the form of KADKLAD R2X3 resin or the like, present inthe composition is 6% (w/w) of the total composition. In anotherexemplary embodiment, the amount of polysilane, in the form of KADKLADR2X3 resin or the like, present in the composition is 3% (w/w) of thetotal composition. In yet another exemplary embodiment, the amount ofpolysilane, in the form of KADKLAD R2X3 resin or the like, present inthe composition is 2% (w/w) of the total composition. In yet anotherexemplary embodiment, the amount of polysilane, in the form of KADKLADR2X3 resin or the like, present in the composition is 1.7% (w/w) of thetotal composition. In still another exemplary embodiment, the amount ofpolysilane, in the form of KADKLAD R2X3 resin or the like, present inthe composition is 1.0% (w/w) of the total composition.

The silicon-based coating compositions of the current invention mayadditionally include one or more organic solvents. Generally, theorganic solvent is defined as a carbon-containing chemical that iscapable of dissolving a solid, liquid, or a gas. Although one skilled inthe art will appreciate that a wide variety of solvents may beincorporated into the current invention, suitable solvents for thepresent invention are those that contain no water and no reactive groupssuch as hydroxyl or amine groups. These solvents include, but notlimited to, for example, aromatic hydrocarbons, such as benzene andtoluene; aliphatic hydrocarbons, such as, hexane, heptane,branched-chain alkanes (isoparaffins); halogenated hydrocarbons; esters,such as methyl acetate, n-butyl acetate, tert-butyl acetate, isobutylacetate, sec-butyl acetate, ethyl acetate, amyl acetate, pentyl acetate,2-methyl butyl acetate, isoamyl acetate, n-propyl acetate, isopropylacetate, ethylhexyl acetate; ketones, such as acetone or methyl ethylketone; ethers, such as tetrahydrofuran, dibutyl ether; acetate ester,such as carboxylic ester where the carboxylic acid component is aceticacid; and mono- and polyalkylene glycol dialkyl ethers (glymes) ormixtures of these solvents may be used. In a preferred embodiment, theorganic solvent comprises n-butyl acetate. In another preferredembodiment, the organic solvent comprises tert-butyl acetate. In yetanother preferred embodiment, the organic solvent comprisesisoparaffins.

In addition, the organic solvent generally comprises between about 20%to about 98% (w/w) of the silicon-based coating composition. In someembodiments, the organic solvent comprises about 98%, about 95%, about90%, about 85%, about 80%, about 75%, about 70%, about 65%, about 60%,about 55%, about 40%, about 35%, about 30%, about 25%, about 20%, (w/w)of the total composition. For example, the amount of organic solventpresent in the silicon-based coating composition preferably ranges frombetween about 80% to about 92% (w/w) of the composition. In anotherembodiment, the amount of organic solvent in the silicon-based coatingcomposition ranges from between about 80% to about 95% (w/w) of thetotal composition. In another embodiment, the amount of organic solventin the silicon-based coating composition ranges from between about 90%to about 98% (w/w) of the total composition. In an additionalembodiment, the amount of organic solvent in the silicon-based coatingcomposition ranges from between about 42% to 54% (w/w) of the totalcomposition. In still another embodiment, the amount of organic solventin the silicon-based coating composition ranges from between about 21%to 43% (w/w). In still another embodiment, the amount of organic solventin the silicon-based coating composition ranges from between about 79%to 89% (w/w).

The silicon-based coating compositions of the current invention mayfurther include one or more organic or inorganic substituents. Theoptional organic or inorganic substituents may be added to introducereactive groups into the reaction and thus to the copolymer. Forexample, by selecting the organochlorosilanes used, the polymerizableside chains of the copolymer may vary. Suitable organochlorosilanes thatmay be added include, but not limited to, chloromethylvinylsilane,chlorodivinylsilane, dichloroethylvinylsilane,dichloromethylvinylsilane, and chloroethylmethyldivinylsilane. The vinylgroups may react with other compounds of low molecular weight that aremixed with the constituents before curing. These changes in the reactionprocess increase the chain length and the degree of three-dimensionalcrosslinking of the resulting macromolecule-networks. As a result, theyhave much higher mass ranges and significantly improved materialproperties.

The silicon-based coating compositions of the current invention mayfurther comprise one or more additives, including, but not limited tocuring agents, pigments, tracing dyes, fillers, flow control agents, dryflow additives, anti-cratering agents, surfactants, texturing agents,light stabilizers, matting agents, photosensitizers, wetting agents,anti-oxidants, plasticizers, opacifiers, stabilizers, ceramicmicrospheres, slip agents, dispersing agents, mica pigments, and surfacealtering additives.

Generally, neither catalyst nor hardener is needed to cure coatings ofthe present invention. In some embodiments of the present invention,each polymer in the composition can be cured independently without theneed of forming co-polymers. In other embodiments, substances ormixtures of substances may be added to a coating composition to promoteor control the curing reaction, for example curing agents such ascatalysts and hardeners. As generally known, curing catalyst increasesthe rate of a chemical reaction as an initiator. It is added in a smallquantity as compared to the amounts of primary reactants, and does notbecome a component part of the chain. In contrast, curing hardener,often an amine, enables the formation of a complex three-dimensionalmolecular structure by chemical reaction between the polymers and theamine. It is essential that the correct mix ratio is obtained betweenresin and hardener to ensure that a complete reaction takes place, suchthat no unreacted resin or hardener will remain within the matrix toaffect the final properties after cure. Conventional polyamine hardenerscomprise primary or secondary amine groups. A polysilazane-modifiedpolyamine hardener was described in U.S. Pat. No. 6,756,469, providingheated polyamine in the presence of a polysilazane to prepare a hardenerimparting enhanced high temperature properties, higher char yields, andbetter adhesion properties.

In a particular embodiment, vinyl groups present in the silicon-basedconstituents may act as reaction promoters, increasing the rate andextent of polymerization of the coating during curing. The vinyl groupsmay be present in any one or more of the constituents of thesilicon-based coating compositions, for example, within the silazane,siloxane, or silane constituent. During polymerization, the vinyl groupsare substantially consumed, forming new covalent bonds withincrosslinked polymer network of the cured coating. The concentration anddistribution of vinyl groups within the coating.

The matting agents used in the practice of this invention typically canalter the surface of a coating in such a way that the light falling onit is scattered in a defined fashion. The matting agent particles standout from the coating, and are invisible to the human eye. The color ofthe coating is not affected to any great extent. Representative examplesof such matting agents include inorganic matting agents such assilica-based ACEMATT® matting agents from Evonik Degussa (Parsippany,N.J.) and silica-based matting agents available from Ineos Silicas(Hampshire, United Kingdom). The matting agents may vary in size andinclude materials that are micron sized particles. For example, theparticles may have an average diameter of from about 0.1 to 1000microns, and in one embodiment from 0.1 to 100 microns. Combinations ofmatting agents may be used.

In addition, the coating composition additives typically comprise lessthan about 30% of the total silicon-based coating composition. In someembodiments, the additive comprises about 30%, about 25%, about 20%,about 15%, about 10%, about 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, 1%, 0.1%, or0% (w/w) of the total composition.

The coating composition may be applied by dipping, spraying, brushing,painting, wiping, immersion, or spin-coating techniques. Theseprocedures typically provide polymer coatings of thicknesses on theorder of 1 μm or thinner, to up to about 75 μm per coat for the curedpolymers. If a thicker coating is desired, multiple coating layers maybe provided. The mold release coat formulations as provided hereinresult in a coating transparent and therefore do not affect the opticalappearance of the substrate, which leaves mold inspection unaffected.Due to the small coating thicknesses, only a very small amount ofmaterial is required, which is advantageous both in terms of cost andalso ecologically, and the weight change of the substrate to be coatedis nearly unnoticeable. The coating thickness of the silicon-basedcoating as provided herein following evaporation of the solvent andcuring is in the range from about 0.1 μm to about 50 μm. In someembodiments the coating thickness is from about 0.5 μm to about 40 μm.In some embodiments, the coating thickness is from about 0.1 μm to about25 μm. In some other embodiments, the coating thickness is from about 1μm to about 3 μm. Yet, in some embodiments, the coating thickness isfrom about 5 μm to about 9 μm. The mold release coating as providedherein can be re-applied onto itself for touch up, repeated applicationover time, or after mold repairs.

“Curing” refers to the process of polymerization after the coating isapplied. Curing may be controlled through temperature, air flow, ratioof the solvents, choice of resin and hardener compounds, and the ratioof said compounds. The curing process can take minutes to hours. Someformulations benefit from heating during the cure period, whereastypically formulation simply require time and ambient temperatures. Inother situation, the curing can be at elevated temperatures to increasethe glass transition (Tg) properties of the finished coating product byenhancing the degree of crosslinking. Coatings ambiently cured may be atroom temperature ranging from 5-40° C. By providing slight amount ofheat the curing time can be shortened. Preferably, curing is performedat temperatures not exceeding about 100° C. Higher temperature may beapplied as needed. The curing atmospheres include, but are not limitedto, air and other non-reactive or reactive gaseous environments whichcontain moisture, inert gases like nitrogen and argon, and reactivegases such as ammonia, hydrogen, carbon monoxide, and so on. Rapid curetimes are achieved using this method when the applied coatings areexposed to the moisture-containing atmosphere at room temperature.

Coating-related testing provides quality control and product descriptionbased on industrial standards. Typical coating tests may include, butnot be limited to, testing thickness, coefficient of friction, hardness,scratch resistance, the amount of force needed to scratch the coatingfrom substrate; 90 degree peel from topcoat test; 90 degree peel fromadhesive test; cross-hatch adhesion test; UV endurance test; heatstability test; conical bend test, impact direct and indirect test. Inparticular, thickness test, measuring the thickness of substrates andtop-coated materials, may be carried out using test panels on whichuniform films are produced by a coating suitable for spraying; usingmicrometers for dried films; using magnetic gauges for nonmagneticcoatings; using Wet Film Thickness Gauge or Pfund Gauge for wet filmthickness; or using microscopic observation of precision angular cuts inthe coating film. Hardness test of organic materials may be carried outusing indentation hardness measurements, Sward-type hardness rockerinstruments, or pendulum damping testers.

In addition, the “kinetic coefficient of friction” (COF, p), also knownas a “frictional coefficient” or “friction coefficient”, describes theratio of the force of friction between two bodies and the force pressingthem together. Coefficients of friction range from near zero to greaterthan one. Rougher surfaces tend to have higher effective values. The COFmeasured under ASTM D1894 is called Standard COF. More standard ASTM(American Society for Testing and Materials) test methods for coatingsare available athttp://wernerblank.com/polyur/testmethods/coating_test.htm. Preferably,in one embodiment, the thickness of the silicon-based coating resultedfrom the compositions provided herein is between from about 0.1 μm toabout 45 μm. In one embodiment, the hardness of the silicon-basedcoating resulted from the compositions provided herein ranges from about4H to about 9H, using ASTM D3363. Further, in one embodiment, the COF ofthe silicon-based coating resulted from the compositions provided hereinis between from about 0.03 to about 0.04.

Mold surfaces, substrates and substrate layers suitable for coatingcompositions provided herein may comprise any desirable substantiallysolid material that vary widely. For example, the type of surfaces thatcan be treated with the compositions of this invention includes glass;fiberglass; carbon fiber composites; basalt fiber composites; siloxaneand ceramic fibers; ceramics, such as, silicon nitride, silicon carbide,silica, alumina, zirconia, and the like; metals, such as, for example,iron, stainless steel, galvanized steel, zinc, aluminum, nickel, copper,magnesium and alloys thereof, silver and gold and the like; plastics,such as, polymethyl methacrylate, polyurethane, polycarbonate,polyesters including polyethylene terephthalate, polyimides, polyamides,epoxy resins, ABS polymer, polyethylene, polypropylene,polyoxymethylene; porous mineral materials, such as, concrete, claybricks, marble, basalt, asphalt, loam, terracotta; organic materials,such as wood, leather, parchment, paper and textiles; and coatedsurfaces, such as, plastics emulsion paints, acrylic coatings, epoxycoatings, melamine resins, polyurethane resins and alkyd coatings. Thesurface or substrate contemplated herein may also comprise at least twolayers of materials. One layer of material, for example, may includeglass, metal, ceramic, plastics, wood or composite material. Otherlayers of material comprising the surface or substrate may includelayers of polymers, monomers, organic compounds, inorganic compounds,organometallic compounds, continuous layers, porous and nanoporouslayers.

Further, the mold surfaces and substrates may have different shapes,e.g., substrates having flat, planar surfaces, molded articles havingcurved surfaces, fibers, fabrics, and the like. It will be appreciatedby those skilled in the art that the foregoing lists are merelyillustrative of various materials which may be coated using thepresently disclosed compositions and methods, and are not in any waylimiting of the different substrates with which the present invention isuseful. Insofar as they protect virtually any type of substrate fromoxidative thermal degradation, corrosion, or chemical attack. Thecoatings may also be used to strengthen relatively flaw sensitivebrittle substrates such as glass and non-wetting surfaces. The coatingsmay additionally be useful to provide bonding or compatibilityinterfaces between different types of materials.

A particularly advantageous, but non-limiting, use of this coating isfor mold surfaces that undergo high pressure and temperature, andmultiple pulls. A protective film provided by the silicon-based coatingcompositions disclosed herein over the base layer of paint or surfacematerial of these mold surfaces is particularly useful to provide longlasting protection, in comparison to other materials in market, fromvarious external forces, which can be destructive over a period of time.Other advantageous, but non-limiting, use of the coatings providedherein is to coat on automobile, aircraft, missiles, aerospacecomponents, marine vessels, wheels, wind generation equipment andblades, engine shrouds, car exhausts, smoke stacks, industrial kilns,combustion chambers, industrial duct and pipe systems, solar panels,electronic components, fire and safety appliance, insulation and energysystems, building surfaces, public spaces, packaging surfaces, outdoorsigns and advertisement billboard or LED screens, food- andbeverage-processing equipment, cookware and containers. Those surfacesare exposed to UV, heat, coldness, moisture, ice build-up, chemicalcorrosion, and wear and tear from natural physical forces creatingfriction such as, water, air flow and dust. In addition, such protectionis particularly suitable for mechanical components exposed to hightemperatures, including, for example, exterior aircraft surfaces, a wingslat or pylon made of titanium, aluminum or cress metal; heat shields onan aircraft or other coated aircraft areas subject to engine efflux. Aprotective film provided by the silicon-based coating compositionsdisclosed herein over the base layer of paint or surface material ofthese surfaces is particularly useful to protect the surface and thesubstrate material from various external forces, particularly from theheat and high temperature, by greatly reducing radiant heat passingthrough the surface and the substrate material.

The cured coating is formed from any of the coating compositionsdescribed herein, and may be cured by any disclosed method, particularlyby exposing the substrate coated with a coating composition to ambientconditions at room temperature for about 24 hours. Within the curedcoating, silicon-based substituents are substantially completely reactedto form new covalent bonds to each other and to the substrate. As such,the coating is substantially free of Si—H bonds, which have beenconsumed in the curing process. Furthermore, if the coating compositioncontained substituents bearing vinyl groups, the C═C bonds are alsoconsumed in the formation of new covalent bonds. Overall, the coatingcomprises a crosslinked polymer network comprising Si—O, Si—N, and Si—Cbonds, especially when both the Si—N and the Si—O bonds are part of thesame polymer network within the coating. Preferably, the coating is alsosubstantially free of ammonia, free amines, or ammonium chloride. Thecrosslinked polymer provides a durable and hard coating, as describedthroughout this specification.

In summary, the silicon-based coatings and coating compositionsdescriber herein serves to rejuvenate the surface and areas below it,thus returning to service obsolete or retired molds that could no longerhold a vacuum; and re-sealing the face side (functional side) of thetooling substrate (versus the back side) in a manner that allows themold to hold a vacuum and allows the mold to create composite partsagain. At the time of invention, no other sealer or mold restorerfunctioned to restore molds on the face side, meeting a long-felt andunmet need in the art. Conventional methods attempted remedy thisproblem (with very limited success) through use of sealers on the backside of the mold using materials such as urethane resins/coatings, suchas truck bed lining material. The cured coatings described herein easilywithstand the operating mold temperatures, and therefore do notdegredate, unlike urethanes under the same operating conditions.Moreover, using the silicon-based coatings described herein do not alterthe dimensional tolerance of the face side of the mold. The presentsilicon-based coatings provide significant cost benefits, because thematerial costs to rejuvenate molds is very reasonable, typicallytotaling less than 5% of the total value of the mold itself. The presentsilicon-based coatings also provide an on-going ability to continue torejuvenate the molds. The silicon-based coating compositions arerecoatable on previously cured silicon-based coating. The operators ofthe molds can continue to extend the life of the molds with periodicapplications the silicon-based coatings.

Although the invention described herein is susceptible to variousmodifications and alternative iterations, specific embodiments thereofhave been described in greater detail above. It should be understood,however, that the detailed description of the composition is notintended to limit the invention to the specific embodiments disclosed.Rather, it should be understood that the invention is intended to coverall modifications, equivalents, and alternatives falling within thespirit and scope of the invention as defined by the claim language.

Definitions

As used herein, the terms “about” and “approximately” designate that avalue is within a statistically meaningful range. Such a range can betypically within 20%, more typically still within 10%, and even moretypically within 5% of a given value or range. The allowable variationencompassed by the terms “about” and “approximately” depends on theparticular system under study and can be readily appreciated by one ofordinary skill in the art.

As used herein, the term “w/w” designates the phrase “by weight” and isused to describe the concentration of a particular substance in amixture or solution.

As used herein, the term “ml/kg” designates milliliters of compositionper kilogram of formula weight.

As used herein, the term “cure” or “curing” refers to a change in state,condition, and/or structure in a material that is usually, but notnecessarily, induced by at least one variable, such as time,temperature, moisture, radiation, presence and quantity in such materialof a catalyst or accelerator or the like. The terms cover partial aswell as complete curing.

As used herein, the term “hardness” or “H” designates the property of amaterial that enables it to resist plastic deformation, usually bypenetration. However, the term hardness may also refer to resistance tobending, scratching, abrasion or cutting. The usual method to achieve ahardness value is to measure the depth or area of an indentation left byan indenter of a specific shape, with a specific force applied for aspecific time. There are four principal standard test methods forexpressing the relationship between hardness and the size of theimpression, these being Pencil Hardness ASTM D3363, Brinell, Vickers,and Rockwell. For practical and calibration reasons, each of thesemethods is divided into a range of scales, defined by a combination ofapplied load and indenter geometry.

As used herein, the term “coefficient of friction” (COF), also known asa “frictional coefficient” or “friction coefficient” or “kineticcoefficient of friction” and is an empirical measurement which describesthe ratio of the force of friction between two bodies and the forcepressing them together. The coefficient of friction depends on thematerials used. When the coefficient of friction is measured by astandardized surface, the measurement is called “standardizedcoefficient of friction”.

As used herein, the term “corrosion resistant agent” or variationthereof refers to additives in the coating on a surface which inhibitthe corrosion of the surface substrate when it is exposed to air, heat,or corrosive environments for prolonged time periods.

As used herein, the term “monomer” refers to any chemical compound thatis capable of forming a covalent bond with itself or a chemicallydifferent compound in a repetitive manner. The repetitive bond formationbetween monomers may lead to a linear, branched, super-branched, orthree-dimensional product. Furthermore, monomers may themselves compriserepetitive building blocks, and when polymerized the polymers formedfrom such monomers are then termed “blockpolymers.” Monomers may belongto various chemical classes of molecules including organic,organometallic or inorganic molecules. The molecular weight of monomersmay vary greatly between about 40 Daltons and 20,000 Daltons. However,especially when monomers comprise repetitive building blocks, monomersmay have even higher molecular weights. Monomers may also includeadditional reactive groups.

Contemplated polymers may also comprise a wide range of functional orstructural moieties, including aromatic systems, and halogenated groups.Furthermore, appropriate polymers may have many configurations,including a homopolymer, and a heteropolymer. Moreover, alternativepolymers may have various forms, such as linear, branched,super-branched, or three-dimensional. The molecular weight ofcontemplated polymers spans a wide range, typically between 400 Daltonsand 400,000 Daltons or more.

The compounds described herein have asymmetric centers. Compounds of thepresent disclosure containing an asymmetrically substituted atom may beisolated in optically active or racemic form. All chiral,diastereomeric, racemic forms and all geometric isomeric forms of astructure are intended, unless the specific stereochemistry or isomericform is specifically indicated.

The term “acyl,” as used herein alone or as part of another group,denotes the moiety formed by removal of the hydroxy group from the groupCOOH of an organic carboxylic acid, e.g., RC(O)—, wherein R is R¹, R¹O—,R¹R²N—, or R¹S—, R¹ is hydrocarbyl, heterosubstituted hydrocarbyl, orheterocyclo, and R² is hydrogen, hydrocarbyl, or substitutedhydrocarbyl.

The term “acyloxy,” as used herein alone or as part of another group,denotes an acyl group as described above bonded through an oxygenlinkage (O), e.g., RC(O)O— wherein R is as defined in connection withthe term “acyl.”

The term “allyl,” as used herein not only refers to compound containingthe simple allyl group (CH₂═CH—CH₂—), but also to compounds that containsubstituted allyl groups or allyl groups forming part of a ring system.

The term “alkyl” as used herein describes groups which are preferablylower alkyl containing from one to eight carbon atoms in the principalchain and up to 20 carbon atoms. They may be straight or branched chainor cyclic and include methyl, ethyl, propyl, isopropyl, butyl, hexyl andthe like.

The term “alkenyl” as used herein describes groups which are preferablylower alkenyl containing from two to eight carbon atoms in the principalchain and up to 20 carbon atoms. They may be straight or branched chainor cyclic and include ethenyl, propenyl, isopropenyl, butenyl,isobutenyl, hexenyl, and the like.

The term “alkynyl” as used herein describes groups which are preferablylower alkynyl containing from two to eight carbon atoms in the principalchain and up to 20 carbon atoms. They may be straight or branched chainand include ethynyl, propynyl, butynyl, isobutynyl, hexynyl, and thelike.

The term “aromatic” as used herein alone or as part of another groupdenotes optionally substituted homo- or heterocyclic conjugated planarring or ring system comprising delocalized electrons. These aromaticgroups are preferably monocyclic (e.g., furan or benzene), bicyclic, ortricyclic groups containing from 5 to 14 atoms in the ring portion. Theterm “aromatic” encompasses “aryl” groups defined below.

The terms “aryl” or “Ar” as used herein alone or as part of anothergroup denote optionally substituted homocyclic aromatic groups,preferably monocyclic or bicyclic groups containing from 6 to 10 carbonsin the ring portion, such as phenyl, biphenyl, naphthyl, substitutedphenyl, substituted biphenyl, or substituted naphthyl.

The terms “carbocyclo” or “carbocyclic” as used herein alone or as partof another group denote optionally substituted, aromatic ornon-aromatic, homocyclic ring or ring system in which all of the atomsin the ring are carbon, with preferably 5 or 6 carbon atoms in eachring. Exemplary substituents include one or more of the followinggroups: hydrocarbyl, substituted hydrocarbyl, alkyl, alkoxy, acyl,acyloxy, alkenyl, alkenoxy, aryl, aryloxy, amino, amido, acetal,carbamyl, carbocyclo, cyano, ester, ether, halogen, heterocyclo,hydroxy, keto, ketal, phospho, nitro, and thio.

The terms “halogen” or “halo” as used herein alone or as part of anothergroup refer to chlorine, bromine, fluorine, and iodine.

The term “heteroatom” refers to atoms other than carbon and hydrogen.

The term “heteroaromatic” as used herein alone or as part of anothergroup denotes optionally substituted aromatic groups having at least oneheteroatom in at least one ring, and preferably 5 or 6 atoms in eachring. The heteroaromatic group preferably has 1 or 2 oxygen atoms and/or1 to 4 nitrogen atoms in the ring, and is bonded to the remainder of themolecule through a carbon. Exemplary groups include furyl, benzofuryl,oxazolyl, isoxazolyl, oxadiazolyl, benzoxazolyl, benzoxadiazolyl,pyrrolyl, pyrazolyl, imidazolyl, triazolyl, tetrazolyl, pyridyl,pyrimidyl, pyrazinyl, pyridazinyl, indolyl, isoindolyl, indolizinyl,benzimidazolyl, indazolyl, benzotriazolyl, tetrazolopyridazinyl,carbazolyl, purinyl, quinolinyl, isoquinolinyl, imidazopyridyl, and thelike. Exemplary substituents include one or more of the followinggroups: hydrocarbyl, substituted hydrocarbyl, alkyl, alkoxy, acyl,acyloxy, alkenyl, alkenoxy, aryl, aryloxy, amino, amido, acetal,carbamyl, carbocyclo, cyano, ester, ether, halogen, heterocyclo,hydroxy, keto, ketal, phospho, nitro, and thio.

The terms “heterocyclo” or “heterocyclic” as used herein alone or aspart of another group denote optionally substituted, fully saturated orunsaturated, monocyclic or bicyclic, aromatic or non-aromatic groupshaving at least one heteroatom in at least one ring, and preferably 5 or6 atoms in each ring. The heterocyclo group preferably has 1 or 2 oxygenatoms and/or 1 to 4 nitrogen atoms in the ring, and is bonded to theremainder of the molecule through a carbon or heteroatom. Exemplaryheterocyclo groups include heteroaromatics as described above. Exemplarysubstituents include one or more of the following groups: hydrocarbyl,substituted hydrocarbyl, alkyl, alkoxy, acyl, acyloxy, alkenyl,alkenoxy, aryl, aryloxy, amino, amido, acetal, carbamyl, carbocyclo,cyano, ester, ether, halogen, heterocyclo, hydroxy, keto, ketal,phospho, nitro, and thio.

The terms “hydrocarbon” and “hydrocarbyl” as used herein describeorganic compounds or radicals consisting exclusively of the elementscarbon and hydrogen. These moieties include alkyl, alkenyl, alkynyl, andaryl moieties. These moieties also include alkyl, alkenyl, alkynyl, andaryl moieties substituted with other aliphatic or cyclic hydrocarbongroups, such as alkaryl, alkenaryl and alkynaryl. Unless otherwiseindicated, these moieties preferably comprise 1 to 20 carbon atoms.

The term “protecting group” as used herein denotes a group capable ofprotecting a particular moiety, wherein the protecting group may beremoved, subsequent to the reaction for which the protection isemployed, without disturbing the remainder of the molecule. Where themoiety is an oxygen atom (and hence, forming a protected hydroxy),exemplary protecting groups include ethers (e.g., allyl, triphenylmethyl(trityl or Tr), p-methoxybenzyl (PMB), p-methoxyphenyl (PMP)), acetals(e.g., methoxymethyl (MOM), β-methoxyethoxymethyl (MEM),tetrahydropyranyl (THP), ethoxy ethyl (EE), methylthiomethyl (MTM),2-methoxy-2-propyl (MOP), 2-trimethylsilylethoxymethyl (SEM)), esters(e.g., benzoate (Bz), allyl carbonate, 2,2,2-trichloroethyl carbonate(Troc), 2-trimethylsilylethyl carbonate), silyl ethers (e.g.,trimethylsilyl (TMS), triethylsilyl (TES), triisopropylsilyl (TIPS),triphenylsilyl (TPS), t-butyldimethylsilyl (TBDMS), t-butyldiphenylsilyl(TBDPS) and the like. When the moiety is an nitrogen atom (and hence,forming a protecting amine) exemplary protecting groups include benzyl,p-methoxyphenyl (PMP), 3,4-dimethoxybenxyl (PMB)), n-silyl groups,esters (e.g., benzoate (Bz), carbonyl (e.g. p-methoxybenzyl carbonyl(Moz), tert-butyloxycarbonyl (BOC), 9-fluorenylmethyloxycarbonyl(FMOC)), acetyl, carbamates, n-silyl groups and the like. A variety ofprotecting groups and the synthesis thereof may be found in “ProtectiveGroups in Organic Synthesis” by T.W. Greene and P.G.M. Wuts, John Wiley& Sons, 1999.

The “substituted hydrocarbyl” moieties described herein are hydrocarbylmoieties which are substituted with at least one atom other than carbon,including moieties in which a carbon chain atom is substituted with aheteroatom such as nitrogen, oxygen, silicon, phosphorous, boron, or ahalogen atom, and moieties in which the carbon chain comprisesadditional substituents. These substituents include alkyl, alkoxy, acyl,acyloxy, alkenyl, alkenoxy, aryl, aryloxy, amino, amido, acetal,carbamyl, carbocyclo, cyano, ester, ether, halogen, heterocyclo,hydroxy, keto, ketal, phospho, nitro, and thio.

When introducing elements of the present disclosure or the exemplaryembodiments(s) thereof, the articles “a”, “an”, “the” and “said” areintended to mean that there are one or more of the elements. The terms“comprising”, “including” and “having” are intended to be inclusive andmean that there may be additional elements other than the listedelements.

Unless otherwise defined, all technical and scientific terms used hereinhave the same meaning as is commonly understood by one of skill in theart to which this invention belongs at the time of filing. Ifspecifically defined, then the definition provided herein takesprecedent over any dictionary or extrinsic definition. Further, unlessotherwise required by context, singular terms shall include pluralities,and plural terms shall include the singular. Herein, the use of “or”means “and/or” unless stated otherwise. All patents and publicationsreferred to herein are incorporated by reference.

The following examples are intended to further illustrate and explainthe present invention. The invention, therefore, should not be limitedto any of the details in these examples.

EXAMPLES Example 1—Preparation of Resin Systems for Making Silicon-BasedCoating Compositions

The silicon-based coating formulations provided herein were formed fromtwo or more different resin systems chosen from, what was known asA-Resin, B-Resin, C-Resin, and any combinations thereof. The A-Resin wasmade according to the formulation provided in Table 1. The A-Resin waspurchased from KiON Defense Technologies (Huntingdon Valley, PA), and itwas sold as KDT HTA® 1500 Fast™, an air curable liquid polysilazanebased coating resin (8.9 lbs/Gallon).

TABLE 1 A-Resin formulation Amount Ingredient CAS NO. (w/w) Appx.Polysilazane CAS# 475645-84-2 <99% (w/w) Cyclosilazane CAS# 503590-70-3 <5% (w/w) n-Butyl acetate CAS# 123-86-4  <3% (w/w) (or tert-Butylacetate) (CAS# 540-88-5) Polysiloxane CAS# 9011-19-2 <50% (w/w)

The B-Resin was made according to the formulation provided in Table 2.The B-Resin was purchased from Genesee Polymers Corp. (Burton, MI), andit was sold as Dimethyl Silicone Fluids G-10 products (8.0 lbs/Gallon).

TABLE 2 B-Resin formulation Amount Ingredient CAS NO. (w/w) Appx.Polydimethylsiloxane fluid CAS# 63148-62-9  <5% (w/w) Isopropyl acetateCAS# 108-24-4 <98% (w/w)

The C-Resin was made according to the formulation provided in Table 3.The C-Resins was purchased from Kadko, Inc. (Beech Grove, Indiana), andit was sold as a polysilazane based KADKLAD R2X3™ product.

TABLE 3 C-Resin formulation Amount Ingredient CAS NO. (w/w) Appx.Polysilane CAS# 475645-84-2  <8% (w/w) Amyl Acetate Blend CAS# 628-63-7<98% Isopropyl acetate CAS# 108-21-4 25-35% Isoparaffnic CAS# 64741-66-850-60% hydrocarbon Aliphatic CAS# 64742-47-8  5-10% hydrocarbon Acetateester CAS# 108419-34-7 1-5%

The A-, B-, and C-Resin systems were then used in appropriate amount fordifferent mold release formulations, as such a mix of polysilazane,polysiloxane and/or polysilane and acetate solvent was used to produceformulations of coating products with various desired properties asdescribed below.

Characteristics of the coating products using the formulations providedherein included extreme release, long lasting, non-transferable, clear,thin, light, slick, hard, high pressure resistant, high temperatureresistant, chemical resistant, and microbial resistant.

Example 2—Mold Release Coat Formulation DT-6025

A mold release silicon-based coating formulation was made according tothe formulation provided in Table 4. The base resin mixture of thisparticular mold release coat was formed by mixing the A-, B- andC-Resins in the amount listed below. The formulation was to be used tocoat the face of a porous composite mold surface.

TABLE 4 Mold Release Silicon-Based Coating DT-6025 CompositionINGREDIENT AMOUNT (w/w) 1. Base Resin Mixture A-Resin:  8% (w/w)B-Resin:  8% (w/w) C-Resin: 73% (w/w) 2. Solvent- tert-Butyl AcetateCAS# 540-88-5  6% (w/w) High-purity Synthetic  5% (w/w) Isoparaffin(Isopar ™-G) Total = 100% (w/w)

To prepare 10 gallons of DT-6025 coating composition, B-Resin andC-Resin were separately agitated, then 0.8 gallons B-Resin were mixedwith 7.3 gallons C-Resin blended using a mix paddle for a few minutes toobtain a uniform mixture. Since both the B- and C-Resin were very fluid,no extreme agitation was required. Next, 0.8 gallons of A-Resin wasadded to the B-Resin/C-Resin mixture, followed by 0.6 gallons oftert-butyl acetate and 0.5 gallons of high-purity synthetic isoparaffin.The complete mixture was thoroughly mixed by stir paddle until ahomogenous or uniform blend was formed. The stir paddle was rotated atabout 500 rpm for about five minutes. The finished formulated resinsystem was then filtered through a 120-mesh paint filter (U.S. standardsieve size) such that no particles or debris were left within thecoating mixture. This filtered resin system was then wiped onto a porousmold surface. The coating had a thickness of about 1 to 2 μm. Thetheoretical coverage of this formulation is 3,000 ft²/gallon for athickness of 0.5 μm. Pre-conditioning of the mold surface can include,for example, drying, cleaning, and removing contamination from thesurface.

After application, the coating was allowed to cure under ambientconditions at room temperature for 25 minutes, after which it was dry totouch, achieving approximately 50% of cured film property values. Afteran additional 24 hours, the finished coating had achieved full propertyvalues. Using comparative tests, including chemical resistance, release,ease of part removal, and tool clean-up, the resultant coating displayedhave superior release properties compared to other industry standardrelease coatings, including better release and easier tool cleanup,among others. The resultant coating was 100% non-transferable tofinished composite part, resulting in reduced mold wear and maintenance,autoclave pressure- and heat durability, pull-resistant, recoatability,crystal clarity, long-term mechanical durable, and ultrathinness. Whentested according to ASTM D3363, the mold release coating had a hardnessof 5H or above.

Example 3—Mold Release Coating Formulation DT-6060

A mold release silicon-based coating formulation was made according tothe formulation provided in Table 5. The mold release coat was formed bymixing the B- and C-Resins in the amount listed below. The formulationwas to be used to coat the face of a metal mold surface.

TABLE 5 Mold Release Silicon-Based Coating DT-6060 CompositionINGREDIENT AMOUNT (w/w) 1. Base Resin Mixture B-Resin: 50% (w/w)C-Resin: 50% (w/w) 2. Solvent- tert-Butyl Acetate CAS# 540-88-5  0%(w/w) Total = 100% (w/w)

To prepare 10 gallons of DT-6060 coating composition, 5 gallons ofB-Resin and 5 gallons C-Resin were thoroughly mixed by stir paddle untila homogenous or uniform blend was formed. The stir paddle was rotated atabout 500 rpm for about five minutes. The finished formulated resinsystem was then filtered through a 120-mesh paint filter (U.S. standardsieve size) such that no particles or debris were left within thecoating mixture. This filtered resin system was then wipe-coated onto ametal mold surface. The applied coating had a thickness of about 1 to 3μm. The theoretical coverage of this formulation is 5,000 ft²/gallon fora thickness of 0.2 μm. Pre-conditioning of the substrate surface caninclude, for example, drying, cleaning, and removing contamination fromthe surface.

After application, the coating was allowed to cure under ambientconditions at room temperature for 25 minutes, after which it was dry totouch, achieving approximately 50% of cured film property values. Afteran additional 24 hours, the finished coating with full property values.The resultant coating was 100% non-transferable to finished compositepart, helped to reduce mold wear. Using comparative tests, includingchemical resistance, release, ease of part removal and tool clean-up,the resultant coating was shown to possess superior release properties,when compared to other industry standard release coatings, such asbetter release and easier tool cleanup among others. The resultantcoating was 100% non-transferable to finished composite part, resultingin reduced mold wear and maintenance, autoclave pressure- and heatdurability, pull-resistant, recoatability, crystal clarity, long-termmechanical durable, and ultrathinness. When tested according to ASTMD3363, the mold release coating had a hardness up to 8H.

Example 4—Mold Release Coating Formulation DT-405

A mold release silicon-based coating formulation was made according tothe formulation provided in Table 5. The base resin mixture of thisparticular mold release coat was formed by mixing the A- and C-Resins inthe amount listed below. The formulation was to be used to coat the faceof a porous composite mold surface.

TABLE 5 Mold Release Silicon-Based Coating DT-405 Composition INGREDIENTAMOUNT (w/w) 1. Base Resin Mixture A-Resin: 50% (w/w) C-Resin: 25% (w/w)2. Solvent- tert-Butyl Acetate CAS# 540-88-5 25% (w/w) High-puritySynthetic  0% (w/w) Isoparaffin (Isopar ™-G) Total = 100% (w/w)

To prepare 10 gallons of DT-405 coating composition, 2.5 gallons ofC-Resin was agitated and then combined with 5 gallons A-Resin and 2.5gallons tert-butyl acetate using a mix paddle until a homogenous oruniform blend was formed. The stir paddle was rotated at about 500 rpmfor about five minutes. The finished formulated resin system was thenfiltered through a 120-mesh paint filter (U.S. standard sieve size) suchthat no particles or debris were left within the coating mixture. Thisfiltered resin system was then wiped onto a porous mold surface. Thecoating had a thickness of about 10 μm to about 38 μm. The theoreticalcoverage of this formulation is 1800 ft²/gallon for a thickness of 25μm. Pre-conditioning of the mold surface included, for example, drying,cleaning, and removing contamination from the surface.

After application, the coating was allowed to cure under ambientconditions at room temperature for 25 minutes, after which it was dry totouch, achieving approximately 50% of cured film property values. Afteran additional 24 hours, the finished coating with full property values.Using comparative tests, including chemical resistance, release, ease ofpart removal and tool clean-up, the resultant coating was shown topossess superior release properties, when compared to other industrystandard release coatings, such as better release and easier toolcleanup among others. The resultant coating was 100% non-transferable tofinished composite part, resulting in reduced mold wear and maintenance,autoclave pressure- and heat durability, pull-resistant, recoatability,crystal clarity, long-term mechanical durable, and ultrathinness. Whentested according to ASTM D3363, the mold release coating had a hardnessof 6H to 9H.

Example 5—Mold Release Coating Formulation DT-201

A mold release silicon-based coating formulation was made according tothe formulation provided in Table 6. The base resin mixture of thisparticular mold release coat was formed by mixing the A-, B- andC-Resins in the amount listed below. The formulation was to be used tocoat the face of a porous composite mold surface.

TABLE 6 Mold Release Silicon-Based Coating DT-201 Composition INGREDIENTAMOUNT (w/w) 1. Base Resin Mixture A-Resin: 66% (w/w) B-Resin: 17% (w/w)C-Resin: 17% (w/w) 2. Solvent- tert-Butyl Acetate CAS# 540-88-5  0%(w/w) High-purity Synthetic  0% (w/w) Isoparaffin (Isopar ™-G) Total =100% (w/w)

To prepare 10 gallons of DT-201 coating composition, the B-Resin andC-Resin were separately agitated. After agitation, 1.7 gallons ofB-Resin and 1.7 gallons of C-Resin were blended using a mix paddle for afew minutes to obtain a uniform mixture. Since both the B- and C-Resinwere very fluid, no extreme agitation was required. Next, 6.6 gallons orA-resin were added to the mixture of B- and C-Resins and was thoroughlymixed by stir paddle until a homogenous or uniform blend was formed. Thestir paddle was rotated at about 500 rpm for about five minutes. Thefinished formulated resin system was then filtered through a 120-meshpaint filter (U.S. standard sieve size) such that no particles or debriswere left within the coating mixture. This filtered resin system wasthen wiped onto a porous mold surface. The coating had a thickness ofabout 10 μm to about 38 μm. The theoretical coverage of this formulationis 1500 ft²/gallon for a thickness of 25 μm. Pre-conditioning of themold surface included, for example, drying, cleaning, and removingcontamination from the surface.

After application, the coating was allowed to cure under ambientconditions at room temperature for 25 minutes, after which it was dry totouch, achieving approximately 50% of cured film property values. Afteran additional 24 hours, the finished coating had full property values.Using comparative tests, including chemical resistance, release, ease ofpart removal and tool clean-up, the resultant coating was shown topossess superior release properties, when compared to other industrystandard release coatings, such as better release and easier toolcleanup among others. The resultant coating was 100% non-transferable tofinished composite part, resulting in reduced mold wear and maintenance,autoclave pressure- and heat durability, pull-resistant, recoatability,crystal clarity, long-term mechanical durable, and ultrathinness. Whentested according to ASTM D3363, the mold release coating had a hardnessof 5H or above.

Example 6—Mold Release Coating Formulation DT-420

A mold release silicon-based coating formulation was made according tothe formulation provided in Table 7. The base resin mixture of thisparticular mold release coat was formed by mixing the A-, B- andC-Resins in the amount listed below. The formulation was to be used tocoat the face of a porous composite mold surface.

TABLE 7 Mold Release Silicon-based Coating DT-420 Composition INGREDIENTAMOUNT (w/w) 1. Base Resin Mixture A-Resin:  9% (w/w) B-Resin:  8% (w/w)C-Resin: 83% (w/w) 2. Solvent- tert-Butyl Acetate CAS# 540-88-5  0%(w/w) High-purity Synthetic  0% (w/w) Isoparaffin (Isopar ™-G) Total =100% (w/w)

To prepare 10 gallons of DT-420 coating composition, the B-Resin andC-Resin were separately agitated, then 0.8 gallons of B-Resin were mixedwith 8.3 gallons of C-Resin using a mix paddle for a few minutes toobtain a uniform mixture. Since both the B- and C-Resin were very fluid,no extreme agitation was required. Next, 0.9 gallons of A-Resin wereadded to the B-Resin/C-Resin mixture. The mixture was thoroughly mixedby stir paddle until a homogenous or uniform blend was formed. The stirpaddle was rotated at about 500 rpm for about five minutes. The finishedformulated resin system was then filtered through a 120-mesh paintfilter (U.S. standard sieve size) such that no particles or debris wereleft within the coating mixture. This filtered resin system was thenwiped onto a porous mold surface. The coating had a thickness of about 5to 9 μm. The theoretical coverage of this formulation is 2200 ft²/gallonfor a thickness of 5 μm. Pre-conditioning of the mold surface included,for example, drying, cleaning, and removing contamination from thesurface.

After application, the coating was allowed to cure under ambientconditions at room temperature for 25 minutes, after which it was dry totouch, achieving approximately 50% of cured film property values. Afteran additional 24 hours, the finished coating had full property values.Using comparative tests, including chemical resistance, release, ease ofpart removal and tool clean-up, the resultant coating was shown topossess superior release properties, when compared to other industrystandard release coatings, such as better release and easier toolcleanup among others. The resultant coating was 100% non-transferable tofinished composite part, resulting in reduced mold wear and maintenance,autoclave pressure- and heat durability, pull-resistant, recoatability,crystal clarity, long-term mechanical durable, and ultrathinness. Whentested according to ASTM D3363, the mold release coating had a hardnessof 6H to 9H.

Example 7—Differential Thermal Analysis of Mold Release Coatings

Differential thermal analysis (DTA) of the tested cured coatingsindicated complete reaction of the resin precursors, giving noindication of free silicon in the coating. This feature is especiallyimportant for mold release coatings. Free silicon may transfer to thesurface of a molded part, leading to issues with adhesion for subsequentprimer and finish coatings on the molded article. The lack of freesilicon in present mold release coatings addresses a long-standing issuewith the current technology. Further, no weight loss of the curedcoating was observed at the tested temperatures.

Two mold release coatings, DT-6060 and DT-420, were prepared asdescribed above in Examples 3 and 6, respectively. DTA was conducted onan aluminum test panel from a temperature of 25° C. to 315° C. with astep increment of 25° C./minutes. Twelve panels were prepared for eachcoating and the results averaged. The relative derivative weight (%) ofeach release coating was plotted against the temperature.

Referring to FIG. 1 , the minimal weight loss below 200° C. can beattributed to the loss of residual solvent in the coating and the lossof moisture adsorbed to the surface from the atmosphere. Free siliconwould have reacted at temperatures between 240° C. and 300° C., whichwould cause a significant decrease of mass due to the loss of lowmolecular weight components. However, this decrease did not occur foreither DT-6060 or for DT-420. No loss of low molecular weight componentswas detected in the temperature range in the DTA. Therefore, bothcoating materials were virtually free of unbound silicon after curingprocess.

Example 8—Comparison of DT-6060 with G-Shield™ Coating Product UsingFTIR Analysis

The Fourier transform infrared (FTIR) spectroscopic analysisdistinguished DT-6060 coatings from G-Shield™ coatings (also known as“Clariant TutoProm”) in at least three significant ways. First, unlikeG-Shield™, DT-6060 coatings did not contain ammonia, free amines orammonium salts, which were byproducts of polysilazane synthesis and areenvironmentally toxic. Second, also unlike G-Shield™, DT-6060 coatingsdid not contain unreacted silanes, indicating a superiorly crosslinkedpolymer network in the coating. Third, DT-6060 coatings contained Si—Oand Si—C, indicating a polysiloxane components within the coating whichis absent from the G-Shield™ coating.

DT-6060 coatings were prepared as described above in Example 3.G-Shield™ is a commercially available product manufactured by KiONSpecialty Polymers (Charlotte, N.C.), a division of Clariant Corporationand a subsidiary of AZ Electronics. G-Shield™ is advertised as a clear,ultrathin, antifouling, protective finish coating, containing aproprietary polysilazane. DT-6060 and G-Shield™ coatings were preparedon an aluminum substrate. Samples were analyzed on Nicholet 380 Fouriertransform infrared spectrometer. Measurements were taken in attenuatedtotal reflectance (ATR) mode with a resolution of 4.000 cm-1 and as anaverage of 128 scans.

FIG. 2 is an FTIR spectrum for the G-Shield™ coating. The N—H stretcharound 3300 cm⁻¹ indicates free ammonia, and the bands around 2800 cm⁻¹and 800 cm⁻¹ indicate the presence of ammonium chloride in the coating.It is also highly probable, based on the FTIR spectrum, that this samplecontains unreacted amines. The G-Shield™ coating further containsunreacted silanes, as indicated by the Si—H stretch at 2128 cm⁻¹. Thepresence of free silanes indicates that the coatings are not fullypolymerized and have not form a fully interconnected polymer network.Problems would also arise if G-Shield™ were used in as a mold releasecoating, because these silanes would transfer to the molded article,potentially causing problems with coating the molded article in upstreamprocessing. While Si—N bonds are quite prevalent, as shown by the strongband at about 900 cm⁻¹, the G-Shield™ coating does not contain any Si—O,Si—C, or vinylic bonds.

FIG. 3 is an FTIR spectrum for the DT-6060 coating formulated in thisinvention. The bands at 3300 cm⁻¹, 2800 cm⁻¹, and 800 cm⁻¹ are absent,indicating no ammonia, free amines, or ammonium chloride in the coating.The Si—O band at 1062 cm⁻¹ and Si—C band at 822 cm⁻¹ are consistent withthe presence of siloxane-containing dimethyl fluid (—Si—(—O—Si—)—_(n))in the DT-6060 coating formulation. Further, the Si—N spectral region(1000-850 cm⁻¹) is significantly broadened compared with the same regionof spectrum for the G-Shield™ coating, indicating a higher degree ofnetworking within the DT-6060 coating than in the G-Shield™ coating. TheSi—O spectral region (1180-1140 cm⁻¹) is also broadened, indicating thatboth the Si—N and the Si—O bonds are part of the same polymer networkwithin the DT-6060 coating. Moreover, DT-6060 does not contain anyunreacted silanes, as indicated by the absence of the Si—H stretcharound 2130 cm⁻¹, suggesting that cured coating is substantiallycompletely reacted.

Based on the analysis of the FTIR spectra, the G-Shield™ coating differssignificantly from DT-6060. First, unlike G-Shield™, the DT-6060 coatingdoes not contain ammonia, free amines or ammonium salts, which areenvironmentally toxic. Second, the silanes in DT-6060 have completelyreacted. Because there are no free Si—H groups, the DT-6060 coatingcomposition formed a significantly more interconnected network duringcuring than did the G-Shield™ coating composition. The peak width of theSi—O and Si—N bands also indicates the extent of the polymer network inthe DT-6060 coating is greater compared to that of the G-Shield™. Thisadvantage is manifested in a shorter drying/curing time for DT-6060coating compared to G-Shield™ coating. The lack of free silanes alsoimproves the non-transferability of the DT-6060 coatings, which isespecially important for mold release applications. Third, becauseDT-6060 contains Si—C and Si—O bonds which are not in the G-Shield™coating material, the two products have different chemical structures,especially the structure of the crosslinked network of the silicon-basedpolymers.

Example 9—FTIR analysis of DT-420, DT-405 and DT-201

Samples of DT-420, DT-405, and DT-201 coatings were also preparedaccording to the present invention and analyzed using FTIR spectroscopy.Coatings for DT-420 were prepared according to Example 6 above, forDT-405 according to Example 4 above, and for DT-201 according to Example5 above. The DT-420, DT-405, and DT-201 coatings were each prepared onan aluminum substrate. Samples were analyzed on a Nicolet 380 Fouriertransform infrared spectrometer. Measurements were taken in ATR modewith a resolution of 4.000 cm-1 and as an average of 128 scans. Spectrafor the DT-420, DT-405, and DT-201 coating samples are shown at FIGS.4-6 , respectively.

As shown in FIGS. 4-6 , these coatings present Si—C bands at 840 cm⁻¹and Si—O bands at about 1165 cm⁻¹. As discussed above in Example 8, theG-Shield™ coating does not containing Si—C or Si—O bonds, meaning thatthe DT coatings are have different chemical structures than theG-Shield™ coatings. Further, the Si—N spectral region (1000-850 cm⁻¹) ofthe DT materials is significantly broadened compared with the sameregion of spectrum for the G-Shield™ coating, indicating a superiordegree of networking within the DT materials. The Si—O spectral region(1180-1140 cm⁻¹) in the DT coatings is also broadened, indicating thatboth the Si—N and the Si—O bonds are part of the same polymer networkwithin the coating. The FTIR for DT-405 and DT-201 coatings (FIGS. 5 and6 ) show bands for ammonia or at free amine and for ammonium.

In summary, the DT-420, DT-405, and DT-201 coatings were structurallydistinct from the G-Shield™ coating. Like the DT-6060 coating, theDT-420, DT-405, and DT-201 coatings comprised a polymer network of Si—Cand Si—O bonds, which G-Shield™ lacks. Moreover, the Si—O and Si—N bondsof the DT coatings are part of the same polymer network, which is notpossible for G-Shield™ coating, because it does not comprise Si—O bonds.

Example 10—Comparison of KDT HTA® 1500 Resin to DT Coatings Using FTIR

KDT HTA® 1500 Resin is an ambient cure coating resin manufactured byKiON Defense Technologies, Inc. (Huntingdon Valley, PA) and provides thepolysilazane constituent in the coating compositions of the presentinvention, as described above in Example 1. FTIR allows for comparisonof the functional groups in the cured DT coatings to the functionalgroups of the uncured KDT HTA® 1500 Resin starting material. Overall,the FTIR spectrum shows that the KDT HTA® 1500 Resin is structurallydistinct from the DT coatings described herein. KDT HTA® 1500 contains arelatively large amount of unreacted Si—H bonds, as well as unreactedvinyl and amine functional groups.

FIG. 7 is an FTIR spectrum for HTA® 1500 Resin as manufactured by KiON.Samples were analyzed on a Nicholet 380 infrared spectrometer.Measurements were taken in ATR mode with a resolution of 4.000 cm-1 andas an average of 128 scans.

The FTIR spectrum for the HTA® 1500 Resin indicates aliphatichydrocarbons at the bands from 2950 cm⁻¹ to 2800 cm⁻¹. The C═C stretchat 1550 cm⁻¹ at indicates partially polymerized vinyl groups, whichpossibly originated from ammonolysis of chlorosilanes during HTA® 1500synthesis. Further, HTA® 1500 Resin contains free amine bonds (N—H), asindicated by the band 3380 cm⁻¹. All together, the HTA® 1500 Resin inthe range of 3-5% ammonium chloride contamination, which was estimatedin relation to the FTIR spectra for standard samples and according tothe integrated peaks for the two FTIR bands corresponding to NH4Cl.

HTA® 1500 Resin also contains Si—H bonds, as indicated by the strongSi—H band at 2117 cm⁻¹. The Si—H bonds are required for networkformation during curing. HTA® 1500 Resin further contains a mixture ofSi—N and Si—O bonds, indicating that the polysilazane that originatedfrom the ammonolysis of chloromethylvinylsilane (or a mixture oforganochlorosilanes) has been processed with a silicone compound, suchas cyclotetrasiloxane or tetramethylcyclotetrasiloxane. In addition, theratio of the bands for —CH₃ (1391 cm⁻¹) and at (1101 cm⁻¹) indicatesthat dimethyl fluid is not a component used to make HTA® 1500 Resin.

In contrast, the C═C stretch at 1650 cm⁻¹ is absent in the spectra forDT coatings which used HTA® 1500 Resin as a constituent, namely DT-420(FIG. 4 ), DT-405 (FIG. 5 ) and DT-201 (FIG. 6 ). (See also Example 9above.) The reactions may involve vinyl groups in DT materials,accounting for a fraction of the observed loss of Si—H signal intensitywhen compared to that of the HTA® 1500 Resin. Such reactions involvingvinyl groups have been observed previously only in the presence of thedivinylplatinum catalysts. Therefore, the siloxane constituent, dimethylsilicone fluids (B-resin), in the DT coating composition may facilitatethe reaction shown in Scheme 1 below:

Scheme 1 presents the addition of a silicon-hydrogen bond (Si—H) to avinyl group of a neighboring chain.

Furthermore, the presence of C—N bands at 1150 cm⁻¹ in the DT-420,DT-405, and DT-201 coatings indicate that the addition of dimethylsilicone fluid enables a methyl exchange reaction, as shown in Scheme 2below:

Considering typical bond dissociation energies, the exchange of N—H (314kJ/mol) and Si—CH₃ (435 kJ/mol) is thermodynamically favored over N—CH₃(770 kJ/mol) and Si—H (298 kJ/mol), releasing a net of −319 kJ/mol ofenergy and thus promoting the crosslinking reactions within the polymernetwork of the coatings. At the same time, new Si—H functionalities arecreated, allowing for subsequent networking reactions.

Without wishing to be bound by theory, the coating compositionsformulated in the present application cure faster than previously knowncoating compositions without requiring additional heat or a transitionalmetal catalyst, which is an advantageous property for silicon-basedcoatings. This increased rate of curing is supported by thethermodynamic calculation for the bond exchange. This enhancedcrosslinking leads to the consumption of vinylic and silane functionalgroups within the coating, and leads to a substantially crosslinkedpolymer network of Si—O, Si—C, and Si—N bonds, especially where the Si—Nand Si—C bonds are part of the same polymer network.

Example 11—Comparison of DT Coatings to Other Coatings Using Coefficientof Friction and Cutting Tests

To determine the benefits of the DT coatings in the present invention incomparison to other finishes, the sample DT-420 coating was applied toStanley HeavyDuty™ 15″ saw blades or TK blades for various test, usingthe coating procedure described above in Example 6. The coefficient offriction (COF), initial sharpness, cutting ability using paper, cuttingability to asphalt shingle, and cutting ability to sheet rock tests wereconducted to compare the DT-420 coating as provide in the presentapplication to coatings such as, Teflon® and lacquer, which arecurrently used.

Coefficient of Friction. Table 8 provides the results of coefficient offriction test, under which the coating materials in comparison wereapplied to Stanley HeavyDuty 15″ saw blades subjecting to 1 lb., 2.5lb., 5 lb., and 10 lb. of pressure. Blades coated with a DT-420 coatingpreformed equivalently to the Teflon®-coated blade, both of which wereabout 70% slicker than the lacquered blades.

TABLE 8 Coefficient of Friction Test Results COF COF COF COF (1 lb. (2.5lb. (5 lb. (10 lb. Sample weight) weight) weight) weight) DT-420 0.2 0.40.8 1.6 Teflon ™ 0.2 0.4 0.8 1.6 Lacquer 0.25 0.6 1.2 2.1 No finish 0.250.55 1.1 2.0

Initial Sharpness. To test initial sharpness of the blades, the numberof strokes needed to cut through a pinewood log was measured for eachsaw blade. The test was repeated for a total of ten runs. The first runwas discarded from each sample set, and the average number of strokeswas calculated for runs 2 through 10, as shown below in Table 9.

TABLE 9 Blade Initial Sharpness Test Cuts on log (Clear Pine) Avg. RunRun Run Run Run Run Run Run Run Run Runs Sample #1 #2 #3 #4 #5 #6 #7 #8#9 #10 2-10 DT-420 53 45 44 48 51 51 50 48 48 36 46.8 Teflon ® 37 37 3838 38 38 37 37 37 38 37.6 Lacquer 39 38 37 36 36 36 36 36 36 36 36.3 Nofinish 37 37 36 37 37 43 43 41 45 46 40.6

The DT-420 coated blades averaged more required strokes per cut than didlacquered blades. Therefore, blades having other coatings had betterinitial sharpness than DT-420 coated blades.

Cutting ability: CATAR STD test is a standardized test procedure toquickly and accurately produce sharpness data for quality control,product evaluation for blade or knife edge. CATAR STD test was used forfurther sharpness measurement of TK blades coated with the DT-6060coating, Teflon®, and lacquer. TK blades coated with the DT-6060 coatingwere prepared following the procedure described above in Example 3. The11-921-60 cut program on the New Britain Plant Catra Paper CuttingMachine was used to perform the testing.

TABLE 10 CATAR Paper Cutting Test Results: First Cut Total 60 SampleDepth Cut Depth DT-6060 36.1 538.6 DT-6060 43.5 534.3 DT-6060 40.0 540.8No finish 44.3 484.4 No finish 44.0 470.8 No finish 45.5 480.3

The first cut of the TK blades with no finish was approximately 10%better than that of TK blades covered with the DT-6060 coating. However,after the initial three cuts the DT-6060 coated TK blades cutapproximately 26% better than uncoated blades.

Cutting ability test using asphalt shingle or sheetrock was conducted toTK blades to show whether the DT-6060 coating can improve the cuttingability of the blades. No significant difference was found between theuncoated and DT-6060 coated blades when the amount of material thatadhered to the blade surface during and after 100 cuts was examined.After 10-100 cuts, the side of the blades covered with DT-6060 coatingshowed minimal amount of asphalt shingle or sheetrock material stickingto the blade, which indicated that the DT-6060 coating does not affectthe cutting ability of a blade. They are non-sticky and thus can avoidcontaminant adhesion the coated surface.

Cookware. In addition, various DT silicon-based coatings have passedmany standard tests used by cookware manufacturers. For example, DTcoatings have passed the 4% lye solution and the 24-hour soak test. DTcoatings also passed the extreme exposure test at 800° F. for 1 hour,showing no delamination of the coating after subsequent cold waterquenching. DT coatings passed 100 dishwasher cycles without loss ofrelease properties. DT coatings also passed the 12 dry egg cook test,where an egg is cooked onto the dry coated surface for three minutes perside at 350° F., immediately washed, and repeated for a total of twelvecycles. The dry egg cook test displayed no loss of release propertiesafter the repeated exposures were observed. DT coatings also passed 40cycles of the Tabor abrasion test, where each cycle consisted of 2,5002-inch long strokes preloaded with 10 pounds of pressure and an abrasivepad change between each cycle, for a total of 100,000 strokes per test.

Example 12—Differential Light Scattering Analysis

Polymerization was determined using differential light scattering (DLS)measurements. DLS can be used to determine particle/molecular size, sizedistribution, and relaxations in complex fluids, especially on thenanomeric and colloidial scales. Random fluctuations of motion in thesample are interpreted in terms of the autocorrelation function (ACF)with the assumption that the measured particles are spherical in shape.

To prepare samples, 5 mL silicon-based material was dissolved in 5 mLhexanes, to which 200 μL MC polymerization initiator was added. Thesamples were allowed to rest at room temperature for two hours, then thesolutions was measured using a 90Plus Particle Size Analyzer(Brookhaven) with a relaxation time (r) of 5.00 s using a verticallypolarized laser light of wavelength 680 nm at a scattering angle of 90°.The DLS measurements were made with the intensity correlation functionmeasured at a temperature of 25° C. with a maximum number of256-channels using a Brookhaven Digital Autocorrelator. Data from theseanalyses are shown in FIGS. 8-15 .

The Si—N-starting material formed monodispersed particles with anaverage diameter of about 1650 nm (1.6 m) (FIGS. 8 & 9 ). TheSi—N—IS-300 material formed particles with bimodal dispersions withaverages at about 1500 nm (1.5 m) and at about 4700 nm (4.7 m) (FIGS. 10& 11 ). The Si—N—MC-3 material formed particles with bimodal dispersionswith averages at about 1 nm and at about 2300 nm (2.3 m) (FIGS. 12 & 13). The Si—N-D68-2 material formed particles with trimodal dispersionswith averages at about 1 nm, at about 600 nm (0.6 m), and at about 4900nm (4.9 m) (FIGS. 14 & 15 ). Of the samples analyzed, Si—N—IS-300provided the most uniform particles (FIGS. 10 & 11 ), and Si—N-D68-2provided the least uniform particles (FIGS. 14 & 15 ).

The performance of coating materials showing trimodal size distributionsare preferred, because they can better adhere to surfaces and formstronger, more complete networks. In particular, the largest fractionforms the initial material framework and determines the physicalproperties directly after applying the material. The middle fraction isprimarily responsible for forming new bonds during crosslinking, whichstrengthens the material and is primarily responsible for the curingprocess. The last fraction comprises low molecular weight components andis necessary to plug the holes in this network and to form the bondswith the surface necessary for adhesion.

While the present invention has been described with respect to preferredembodiments, it will be apparent to those skilled in the art that thedisclosed invention may be modified in numerous ways and may assume manyembodiments other than those specifically described above. Accordingly,it is intended by the appended claims to cover modifications of theinvention that fall within the true spirit and scope of the invention.

1-76. (canceled)
 77. A cured silicon-based coating formed by coatingonto a surface a silicon-based composition comprising 1% to 76% (w/w ofthe total composition) polysilazane, 1% to 9% (w/w of the totalcomposition) polysilane, 0.2% to 4% (w/w of the total composition)polysiloxane, and at least one organic solvent; wherein the polysilazaneis of a formula (R₁R₂SiNH)_(n), wherein n is 2 or more, and wherein R₁and R₂ are the same or different and are chosen from alkyl, alkenyl,cycloalkyl, alkylamino, aryl, aralkyl, or alkylsilyl; and wherein thepolysilane is of a formula (R₁R₂Si)_(n), wherein n is greater than 1,and wherein R₁ and R₂ are the same or different and are chosen fromalkyl, alkenyl, cycloalkyl, alkylamino, aryl, aralkyl, or alkylsilyl;and (b) curing the coating ambiently to provide the coating.
 78. Asilicon-based coating composition comprising: 1% to 76% (w/w of thetotal composition) polysilazane of a formula (R₁R₂SiNH)_(n), wherein nis 2 or more, and wherein R₁ and R₂ are the same or different and arechosen from alkyl, alkenyl, cycloalkyl, alkylamino, aryl, aralkyl, oralkylsilyl; 1% to 9% (w/w of the total composition) polysilane of aformula (R₁R₂Si)_(n), wherein n is greater than 1, and wherein R₁ and R₂are the same or different and are chosen from alkyl, alkenyl,cycloalkyl, alkylamino, aryl, aralkyl, or alkylsilyl; 0.2% to 4% (w/w ofthe total composition) polysiloxane; and at least one organic solvent.79. The composition of claim 78 further comprising 0.5% (w/w of thetotal composition) to 2.5% (w/w of the total composition) acetate ester.80. The composition of claim 78, wherein the polysilazane is cyclicpolydimethylsilazane.
 81. The composition of claim 78, wherein thepolysiloxane is polydimethylsiloxane.
 82. The composition of claim 78,wherein the polysilane is polydimethylsilane.
 83. The composition ofclaim 78, wherein the solvent is isopropyl acetate and petroleumdistillates.
 84. The composition of claim 78 comprising: 1% to 4% (w/wof the total composition) cyclic polydimethylsilazane; 1% to 9% (w/w ofthe total composition) polydimethylsilane of a formula (R₁R₂Si)_(n),wherein n is greater than 1, and wherein R₁ and R₂ are each methyl; 0.2%to 4% (w/w of the total composition) polydimethylsiloxane; and 79% to97% (w/w of the total composition) organic solvent chosen from isopropylacetate, petroleum distillates, and combinations thereof.
 85. A curedsilicon-based coating, the coating formed from a mixture of constituentscomprising: 1% to 76% (w/w of the total composition) polysilazane; 0.2%to 4% (w/w of the total composition) polysiloxane; 1% to 9% (w/w of thetotal composition) polysilane of a formula (R₁R₂Si)_(n), wherein n isgreater than 1, and wherein R₁ and R₂ are the same or different and arechosen from alkyl, alkenyl, cycloalkyl, alkylamino, aryl, aralkyl, oralkylsilyl; and at least one organic solvent; wherein the coating issubstantially free of Si—H bonds, and wherein the coating comprises apolymer network comprising Si—O bonds and Si—C bonds.
 86. The curedsilicon-based coating of claim 85, the coating formed from a mixture ofconstituents comprising: 1% to 4% (w/w of the total composition) cyclicpolydimethylsilazane; 1% to 9% (w/w of the total composition)polydimethylsilane of a formula (R₁R₂Si)_(n), wherein n is greater than1, and wherein R₁ and R₂ are each methyl; 0.2% to 4% (w/w of the totalcomposition) polydimethylsiloxane; and 79% to 97% (w/w of the totalcomposition) organic solvent chosen from isopropyl acetate, petroleumdistillates, and combinations thereof; wherein the coating issubstantially free of Si—H bonds, and wherein the coating comprises apolymer network comprising Si—O bonds and Si—C bonds.
 87. Asilicon-based coating composition, comprising: 1% to 76% (w/w of thetotal composition) polysilazane; 1% to 9% (w/w of the total composition)polysilane of a formula (R₁R₂Si)_(n), wherein n is greater than 1, andwherein R₁ and R₂ are the same or different and are chosen from alkyl,alkenyl, cycloalkyl, alkylamino, aryl, aralkyl, or alkylsilyl; 0.2% to4% (w/w of the total composition) polysiloxane; and at least one organicsolvent.
 88. The composition of claim 87 further comprising 0.5% (w/w ofthe total composition) to 2.5% (w/w of the total composition) acetateester.
 89. The composition of claim 87, wherein the polysilazane iscyclic polydimethylsilazane.
 90. The composition of claim 87, whereinthe polysiloxane is polydimethylsiloxane.
 91. The composition of claim87, wherein the polysilane is polydimethylsilane.
 92. The composition ofclaim 87, wherein the solvent is isopropyl acetate and petroleumdistillates.
 93. The composition of claim 87 comprising: 1% to 4% (w/wof the total composition) cyclic polydimethylsilazane; 1% to 9% (w/w ofthe total composition) polydimethylsilane of a formula (R₁R₂Si)_(n),wherein n is greater than 1, and wherein R₁ and R₂ are each methyl; 0.2%to 4% (w/w of the total composition) polydimethylsiloxane; and 79% to97% (w/w of the total composition) organic solvent chosen from isopropylacetate, petroleum distillates, and combinations thereof.
 94. A curedsilicon-based coating formed from a mixture of constituents comprising:1% to 76% (w/w of the total composition) polysilazane; 0.2% to 4% (w/wof the total composition) polysiloxane; 1% to 9% (w/w of the totalcomposition) polysilane of a formula (R₁R₂Si)_(n), wherein n is greaterthan 1, and wherein R₁ and R₂ are the same or different and are chosenfrom alkyl, alkenyl, cycloalkyl, alkylamino, aryl, aralkyl, oralkylsilyl; and at least one organic solvent; wherein the coating issubstantially free of Si—H bonds, and wherein the coating comprises apolymer network comprising Si—O bonds and Si—C bonds.
 95. The curedsilicon-based coating of claim 94, the coating formed from a mixture ofconstituents comprising: 1% to 4% (w/w of the total composition) cyclicpolydimethylsilazane; 1% to 9% (w/w of the total composition)polydimethylsilane of a formula (R₁R₂Si)_(n), wherein n is greater than1, and wherein R₁ and R₂ are each methyl; 0.2% to 4% (w/w of the totalcomposition) polydimethylsiloxane; and 79% to 97% (w/w of the totalcomposition) organic solvent chosen from isopropyl acetate, petroleumdistillates, and combinations thereof; wherein the coating issubstantially free of Si—H bonds, and wherein the coating comprises apolymer network comprising Si—O bonds and Si—C bonds.